Process for dyeing vinyl resin textile articles



Patented Dec. 11, 1951 PROCESS FOR DYEING VINYL RESIN TEXTILE ARTICLES Theophilus A. Feild, Jr., Charleston, W. Va., assignor to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application June 11, 1946, Serial No. 676,099

Claims. (Cl. 8-17) This invention relates to improvements in the dyeing of filaments, yarns and other textile articles made from certain water-insoluble vinyl resins; and more especially it concerns a novel process for the production of dyed textile articles made from copolymers of a, vinyl halide and a vinyl ester of an aliphatic acid, and those made from after-chlorinated copolymers of that type. The invention has especial utility. for the production from filaments, yarns, etc. made of or comprising resins resulting from the conjoint polymerization of vinyl chloride and vinyl acetate, as described in United States Patent No. 2,161,766, of dyed articles possessing fully developed colors, and good wash fastness and crock fastness, while retaining the strength, elongations and other important physical properties necessary to adapt such articles for commercial uses.

Textile articles made from resins of the aforesaid types, such as the vinyl halide-vinyl acetate v copolymer resins, which are not readily permeable to water, cannot be dyed satisfactorily by the usual dyeing procedures employed in dyeing cotton, wool, natural silk, and organic derivatives of cellulose such as regenerated cellulose and cellulose acetate, which are not water-resistant. When dyeing textile articles made from the said resins at temperatures low enough to preclude excessive shrinkage, either the dye does not penetrate the material or, when some limited degree of penetration is efiected, the dye is not fast and leaches out during scouring and other processing operations. Prior to this invention it has been considered necessary, for the proper dyeing of these water-resistant materials, to employ in the dyebath liquids which swell or have a mild solvent action upon the resin forming the textile article so as to permit the dye more readily to enter the latter. However, such solvents, at best, are difiicult to use and control, and may cause weakening of the textile article.

It already is known that the intensity of the dyeing effect upon an article often can be increased by raising the temperature of the dyebath or by using longer immersion times. However, when dyeing stretched filaments and yarns of thermoplastic materials, the maximum temperature of the dyebath must be kept below that at which serious shrinkage of the article occurs. The maximum dyebath temperature which safely may be used depends upon such factors as the softening temperature of the fibers or yarn and the time of exposure to the dyebath. In the case of the vinyl halide-vinyl acetate copolymer yarns it generally is around 65' C. or less, due to the low strain release temperature of such yarn.

Among the more important objects of this invention are the following: to provide for dyeing yarns and other textile articles made of or containing water-resistant thermoplastic resins in a manner to obtain full color development in such articles, together with good wash fastness and crock fastness; \to provide for dyeing such textile articles involving the use of dyes and colors previously not useful for dyeing such articles in the absence of solvent dyeing assistants, unless using dyeing conditions permitting undue shrinkage or weakening of the yarn or other article; and to provide for dyeing such yarns and other textiles made from vinyl chloride-vinyl acetate copolymer resins and from after-chlorinated copolymer resins of this type, using acetate-type, basic-type and oil soluble-type dyestuffs. Thelatter show little aifinity for such resins at dyeing temperatures heretofore considered practical, and are largely removable therefrom in the usual scouring operation.

According to a preferred form of the invention, a yarn, fiber or filament made from or containing a water-resistant vinyl resin of the foregoing type is first treated with a solution of a dyestufi in a volatile liquid non-solvent for the resin forming the yarn, the dye applying oath generally being at a temperature within the range from room temperature to around 60 C. This treatment causes deposition of a thin film or layer of the dyestuff upon the surface of the yarn.

To facilitate uniform intimate contact between the yarn and the treating bath containing the dye, the bath may contain a wetting agent, such as an alkali metal salt of a higher alkyl sulfate or other surface tension depressant, or the surface of the yarn first may be wetted by immersion of the yarn in water containing such a wetting agent, and then immersed in the treating bath. Very brief periods of exposure of the yarn to the treating bath are quite effective. at temperatures ranging from room temperature to around 60 C. or more.

Among non-solvents for the resin which are useful in preparing the dyebath may be mentioned water, various alcohols such as methanol, ethanol, isopropanol, and the higher alkanols; and various aliphatic hydrocarbons and mixtures thereof, such as heptane, octane and higher a1- kanes, mineral spirit, and an aliphatic hydrocarbon mixture boiling within the range between 93 C.- C. Mixtures of thes non-solvents may be used.

The initial dyeing operation may be conducted in various ways. Thus, yarn to be dyed, preferably having a low degree of twist, for example, three or less turns per inch, may be passed continuously from'a source of supply through the treating bath where it is coated with color. The coated yarn then is wound continuously on bobbins for storage prior to the subsequent fixing step hereinafter described, or it is immediately conducted to the dye-fixing operation. On the otherhand,'cakesorskeinsofthe.yarnsmaybe submerged in the solution of dyestuif for a time suilicient to coat the yarn.

The thus coated yarn then is briefly upoeed to an elevated temperature of"at immos' C. while under tension at least suflicient to preventsuhstantial shrinkage of the yarn. This preferably is accomplished during continuous movement of the coated yarn through a heated dye-fixing some. instances where the yarn is unstretched prior to the dye-coating step, the coated unoriented yarn, while exposed to an elevated dyefixing temperature preferably within the range between 105 C. and 200 C., is stretched an amount sufllcient to increase its tenacity to at least two grams per denier. and to reduce its elongation to around 10% to 30%. The conditions of the stretching operation simultaneously i'lx the color in the stretched yarn. when yarns having an initial low degree of stretch or fully stretched yarns are to be colored or dy d. the yarns from the dye applying step are passed directly through the heated dye-fixing zone while under tension at least sufllcient to prevent substantial shrinkage of the yarn and, when desired, under conditions imparting an additional amount of stretch to the yarn being dyed,

Excellent fixation of acetate-type dyestuffs, basic-type dyestuffs and oil soluble-type dyestuffs in yarns and other textile articles made from water-resistant vinyl resins of theforegolng types is secured by the use of dry heat or of steam, at temperatures within the .range between 105' C. and 200 C. When using steam, temperatures around 105' C. to 150 C. are preferred.

Although the coated yarns being passed con tinuously through the dye applying bath may be conducted while wet directly to the dye-fixing zone, best results usually are obtained where the coated yarns are dried at temperatures substantially below the softening point of the resin yarn, and preferably at temperatures no higher than around 60 C., before moving'to the dyeflxing operation.

The amount of dye ilxed upon the yarn varies with the time of exposure of the yarn to the 11xing heat, and with the temperature of the heating means. Generally, excellent dyeing results are obtained, while minimizing dyestuif losses during subsequent scouring of the dyed yarn,

. when the solution of dyestuf! contains between D estui! Dye ype Solvent g g g .Liter Astra Phioxine FF Extra... Basic Water..... 10 vlcntgria Blue BA (0. I. .....do Ethanol... 10 10 d 10 do ..do 10 Troluoil... 10 National Oil .....do o Caleo Oil Orange Y-203-... .....do .do... 6

The following examples serte to illustrate the invention: 1 trample I Unstretched 435-denier yarn, formed from a vinyl chloride-vinyl acetate copolymer ruincontaining90% ofthechlorideinthepolymerand having a macromolecular weight or around 25,000, was passed at a speed of 17.8 yards per minute through an aqueous solution containing 10 grams of Astra-Phloxine F1" Extra per liter of water, maintained at a temperature of 25' C. The time of exposure of the yarn to the dye applying bath was about 0.5 second. After drying the yarn at a temperature around 25' C. the coated yarn was passed at a rate of 55 yards per minute through a 15-inch steam c ber maintained at 125 C., while imparting to the yarn a stretch of 468% of its original length. The stretched yarn then was wound upon bobbins in well-known manner. It was dyed a brilliant pink. The wash fastness and crock fastness oi the dyed yam were excellent.

Example I! A 420-denier vinyl chloride-vinyl acetate copolymer unstretched yarn of the general type described in Example I was passed continuously at a rate of 8.75 yards per minute through a dye applying bath prepared by treating 5 grams of Eastone Rubine C with 250 cc. of ethyl alcohol, and discarding the residue formed. The dyebath was maintained at a temperature of 25" C.. and the time of exposure of the yarn to the dyebath was about 0.5 second. The thus coated yarn was dried and given a twist of 8 turns per inch (Z), and then was passed rapidly through a 15-inch steam chamber maintained at 125 C. and stretched 463% of its original length in the presence of steam. The resultant stretched yarn was dyed to a full rubine shade.

Example In A bobbin of GOO-denier unstretched vinyl chloride-vinyl acetate copolymer yarn having an 8 turns per inch (2) twist was stretched 463% of its length in the presence of steam while passing through a 15-inch steam chamber maintained at 125 C. The vinyl resin from which the yarn was made contained 90% of the chloride in the polymer and had a macromolecular weight of about 25,000.

The resultant stretched yarn was drawn at a rate of I'M/yards per minute through a solu-.

tion of Calco 011 Yellow 7463 (C. I. 19) in a mixture of aliphatic hydrocarbons boiling between 93 C. and 115 C., and containing 10 grams of the dyestuf! per ,liter of the solution. The coated yarn then was passed under tension at a rate of 137 yards per minute through a 15-inch steam chamber maintained at 110 C.,-the time of exposure to this heat being 0.18 secondthereby imparting to the yarn an additional stretch of 3%. The yarn then was wound upon bobbins. After passing the steam chamber, the dyestuif was fixed uniformly on the yarn; and the dyed yarn was fast to washing and crocking. The tensile properties of the yarn were not im Example IV Example V A 100-denier unstretched yarn having a wet tenacity of less than 1.0 gram per denier with an elongation of over 100%, and formed from an after-chlorinated vinyl chloride-vinyl acetate copolymer resin having about 60% of chlorine in I the polymer, was passed continuously through a solution of Calco Oil- Orange Y-293 in a mixture of aliphatic hydrocarbons boiling between 93 C. and 115 C. and having a concentration of 6 grams of the dyestufi per-liter of solution,

. and maintained at a temperature of 25 C. The

thus coated yarn as it left the dyebath was stretched 510% of its original length while passing through a radiant heater 28 inches long and maintained at 181 C. The yam entered the dye fixing zone at a rate of 16.4 yards per minute. The resultant yarn was coned, knitted into a fabric, and tested for wash fastness and physical properties. The wash and crock fastness were excellent. The finished yarn had a denier of 16,

a wet tenacity of 2.59 grams per denier, and an elongation of 16.2%.

By the practice of this invention filaments and yarns made from water-insoluble vinyl resins such as the copolymers of vinyl halides with vinyl esters of aliphatic acids, and those made from corresponding after-chlorinated copolymers, may be effectively dyed by means of acetate-type, basictype and oil soluble-type dyestuffs, yielding dyed products having excellent wash fastness and crock fastness while retaining or actually increasing the tenacities and other important physical properties possessed by the undyed filaments and yarns. These valuable results are secured without recourse to the use of a solvent or softening agent for the resin of which the filaments and yarns are made.

The invention is susceptible of modification within the scope of the appended claims.

I claim:

1. Process for dyeing textile filaments and yarns made from a resinous copolymer selected from the class consisting of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, and after-chlorinated copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, to provide a dyed article of good wash fastness and crock fastness. while improving the tenacity and other physical properties of such dyed article, which comprises subjecting such a filament or yarn to a solution of a dyestuff selected from the class consisting of acetate-type, basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for said copolymer and is maintained at a temperature substantially below the softening point of the copolymer yarn, thereby depositing a thin film of the dyestuff upon the surface of the yarn, while preventing release of any internal strains present in said yarn, and thereafter exposing the coated yarn for a brief time interval to heat maintained at a temperature within the range between around C. and around 200 C., while concurrently stretching the coated yarn, thereby simultaneously increasing the strength of the yarn, reducing the elongation of the yarn, fixing the dye within the yarn, and providing a dyed product having good wash fastness and crock fastness.

2. Process for dyeing textile filaments and yarns made from a resinous copolymer selected from the class consisting of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, and after-chlorinated copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, to provide a dyed article ofgood wash fastness and crock fastness, while improving the tenacity and other physical properties of such dyed article, which comprises briefiy subjecting such a filament or yarn to a solution of a dyestuil. selected from the class consisting of acetatetype, basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for said copolymer and is maintained at a temperature not substantially higher than about 65 0.. thereby depositing a thin film of the dyestuff upon the surface of the yarn while preventing release of any internal strains present in said yarn, drying the coated yarn at a temperature below the softening point thereof, and thereafter exposing the dry coated yarn for a brief time interval to heat maintained at a temperature within the range between around 105 C. and around 200 C., while concurrently stretching the coated yarn, thereby simultaneously increasing the strength of the yarn, reducing the elongation of the yarn, fixing the dye within the yarn, and providing a dyed product having good wash fastness and crock fastness.

3. Process for dyeing textile filaments and yarns made from a resinous copolymer selected from the class consisting of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, and after-chlorinated copolymers of a vinyl halide and a vinyl ester of an aliphatic acid, to provide a polymer and is maintained at a temperature not substantially higher than about 65C thereby depositing a thin film of the dyestuif upon the surface of the yarn while preventing release of any internal strains present in said yarn, and thereafter exposing successive portions of the coated yarn for a brief time interval to heat maintained at a temperature within the range between around 105 C. and around C., in the presence of steam, while concurrently stretching the coated yarn, thereby simultaneously increasing the strength of the yarn, reducing the elongation of the yarn, fixing the dye within the yarn, and providing a dyed product having good wash fastness and crock fastness.

4. Process for dyeing textile filaments and yarns made from a resinous copolymer selected from the class consisting of copolymers of a vinyl halide with a vinyl ester of an aliphatic.

acid and such copolymers which have been afterchlorinated, to provide a dyed article of good wash fastness and crock fastness, which comprises subjecting such a filament or yarn to a solution of a dyestufl selected from the class consisting of acetate-typ basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for the said copolymer and is maintained at a. temperature not substantially higher than 65 C., thereby depositing a thin film of the dyestuff upon the surface of the yarn, while preventing release of any internal strains present in said yarn, drying the coated yarn at a temperature below the softening point thereof, and exposing the successive portions of dry coated yarn for a brief interval to an elevated temperature within the range between around 105 C. and around 200 C., while' the yarn is under tension at least sufilcient to prevent substantial shrinkage of the yarn, thereby fixing the dyestufl in the yarn and providing a dyed yarn having fully developed color, and good wash fastness and crock fastness.

5. Process for dyeing textile filaments and yarns made from copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, and from such copolymers which have been after-chlorinated, to provide a dyed article of good wash fastness and crock fastness, which comprises rapidly passing such a filament or yarn through a solution of a dyestufi selected from the class consisting of acetate-type, basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for the said copolymer and is maintained at a temperature no higher than 60 C., thereby depositing a thin coat of the dyestuif on the yarn, withdrawing the coated yarn from the dyebath and exposing successive portions thereof for a brief interval to an elevated temperature within the range between around 105 C. and around 200 C. while the yarn is under tension at least sufllcient to prevent substantial shrinkage of the yarn, thereby fixing the dyestuflf in the yarn and providing a strong dyed yarn having fully developed color, and good wash fastness and crock fastness.

6. Process for dyeing stretched textile filaments and yarns made from copolymers of a vinyl halide with a vinyl ester of an aliphatic acid and from such copolymers which have been after-chlorinated, to provide a dyed article of good wash fastness and crock fastness, which comprises passing such a filament or yarn rapidly through a solution of a dyestufi selected from the class consisting of acetate-type, basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for the said copolymer and maintained at a temperature no higher than 60 C., thereby depositing a thin filnr of the dyestuff on the yarn, withdrawing the coated yarn from the dyebath and exposing successive portions thereof for a brief interval to an elevated temperature within the range between around 105 C., and 150 C., in the presence of steam, while the yarn is under tension at least suflicient to prevent substantial shrinkage of the yarn, thereby fixing the dyestutf in the yarn and providing a strong dyed yarn having fully developed color, and good wash fastness and crock fastness.

7. Process for dyeing stretched textile filaments and yarns made from a vinyl resin selected from the class consisting of the copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, and after-chlorinated copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, to produce a dyed article of good wash fastness and crock fastness while at least maintaining the tenacity and elasticity possessed by the undyed filaments and yarns, which comprises subjecting such a stretched filament or yarn to a solution of a dyestuff selected from the class consisting of the acetate-type, basic-type and oil soluble-type dyestuffs. which solution is substantially free from components having a solvent action on said vinyl resin and is maintained at a temperature substantially below the softening point of such resin. thereby depositing a thin film of the dyestuff upon the surface of the yarn while preventing the release of any internal strains present in said yarn, and thereafter exposing successive portions of the coated stretched yarn for a brief time interval to a source of heat maintained at a temperature within the range between around C. and around 200 C. while maintaining the yarn under a tension at least sufiicient to prevent substantial shrinkage thereof. thereby fixing the dyestufi in the yarn and providing a dyed yarn having fully developed color, and good wash fastness and crock fastness, and having a tenacity at least as great as that possessed by the undyed yarn.

8. Process for dyeing textile filaments and yarns made from resinous copolymers of a vinyl halide with a vinyl ester of an aliphatic acid and from such copolymers which have been afterchlorinated, to provide a dyed article of good wash fastness and crock fastness, which comprises briefly passing successive portions of a filament or yarn formed from such a resinous copolymer through a solution of a dyestufl selected from the class consisting of the acetatetype, basic-type and oil soluble-type dyestuffs, which solution is substantially free from solvents for said resin and maintained at a temperature not substantially higher than 65 C., drying the thus coated yarn at a temperature substantially below the softening temperature of the resin, and stretching successive portions of the coated yarn at least 10% while concurrently briefly passing successive portions thereof through a high temperature dye-fixing zone maintained at between around 105 C. and around 200 C., thereby simultaneously fixing the dyestuif in said yarn and at least maintaining the tenacity of the yarn and providing a strong, elastic dyed yarn having fully developed color and good wash fastness and crock fastness.

9. Process as defined in claim 8 wherein the filament or yarn moving to the dyestuff solution has been at least partially oriented by a stretching operation at an elevated temperature below softening point of the resinous copolymer.

10. Process for dyeing textile filaments and yarns made from a resinous copolymer selected from the class consisting of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid and after-chlorinated copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, to provide a dyed article of good wash fastness and crock fastness while improving the tenacity and other physical properties of such article, which comprises subjecting such a filament or yarn to a solution of a dyestuf! having a low affinity for such copolymer at temperatures of 65 C. or'below in the absence of dyeing assistants but which penetrates the surface of the copolymer filament or yarn when exposed briefly to temperatures between 105 C. and 200 C., which solution is substantially free from solvents for said copolymer and is maintained at a temperature not substantially higher than 65 C., thereby depositlng a thin film of the dyestuff upon the surface of the yarn, while preventing release of any internal strains present in said yarn, and

thereafter exposing the coated yarn for a brief time interval to heat maintained at a temperature within the range between around 105 C. and around 200 C., while concurrently stretching the coated yarn, thereby simultaneously increasing the strength of the yarn, reducing the elongation of the yarn, fixing the dye within the yarn, and providing a dyed product having good wash fastness and crock fastness.

THEOPHILUS A. FEILD, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,080,254 Dreyfus May 11, 1937 2,232,460 Klein Feb. 18, 1941 5 2,321,746 Heymann June 15, 1943 2,347,508 Rugeley Apr. 25, 1944 OTHER REFERENCES American Dyestuflf Reporter for Oct. 27, 1941, 10 pp. 575 and 5'78. 

1. PROCESS FOR DYEING TEXTILE FILAMENTS AND YARNS MADE FROM A RESINOUS COPOLYMER SELECTED FROM THE CLASS CONSISTING OF COPOLYMERS OF A VINYL HALIDE WITH A VINYL ESTER OF AN ALIPHATIC ACID, AND AFTER-CHLORINATED COPOLYMERS OF A VINYL HALIDE WITH A VINYL ESTER OF AN ALIPHATIC ACID, TO PROVIDE A DYED ARTICLE OF GOOD WASH FASTNESS AND CROCK FASTNESS, WHILE IMPROVING THE TENACITY AND OTHER PHYSICAL PROPERTIES OF SUCH DYED ARTICLE, WHICH COMPRISES SUBJECTING SUCH A FILAMENT OF YARN TO A SOLUTION OF A DYESTUFF SELECTED FROM THE CLASS CONSISTING OF ACETATE-TYPE, BASIC-TYPE AND OIL SOLUBLE-TYPE DYESTUFFS, WHICH SOLUTION IS SUBSTANTIALLY FREE FROM SOLVENTS FOR SAID COPOLYMER AND IS MAINTAINED AT A TEMPERATURE SUBSTANTIALLY BELOW THE SOFETNING POINT OF THE COPOLYMER YARN, THREBY DEPOSITING A THIN FILM OF THE DYESTUFF UPON THE SURFACE OF THE YARN, WHILE PRVENTING RELEASE OF ANY INTERNAL STRAINS PRESENT IN SAID YARN, AND THEREAFTER EXPOSING THE COATED YARN FOR A BRIEF TIME INTERVAL TO HEAT MAINTANED AT A TEMPERATURE WITHIN THE RANGE BETWEEN AROUND 105* C. AND AROUND 200* C., WHILE CONCURRENTLY STRETCHING THE COATED YARN, THEREBY SIMULTANEOUSLY INCREASING THE STRENGTH OF THE YARN, REDUCING THE ELONGATION OF THE YARN, FIXING THE DYE WITHIN THE YARN, AND PROVIDING A DYED PRODUCT HAVING GOOD WASH FASTNESS AND CROCK FASTNESS. 